CN101663352B - Rubber combination and use its pneumatic tyre - Google Patents
Rubber combination and use its pneumatic tyre Download PDFInfo
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- CN101663352B CN101663352B CN200880013148.1A CN200880013148A CN101663352B CN 101663352 B CN101663352 B CN 101663352B CN 200880013148 A CN200880013148 A CN 200880013148A CN 101663352 B CN101663352 B CN 101663352B
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L7/00—Compositions of natural rubber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0008—Compositions of the inner liner
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0016—Compositions of the tread
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B60—VEHICLES IN GENERAL
- B60C—VEHICLE TYRES; TYRE INFLATION; TYRE CHANGING; CONNECTING VALVES TO INFLATABLE ELASTIC BODIES IN GENERAL; DEVICES OR ARRANGEMENTS RELATED TO TYRES
- B60C1/00—Tyres characterised by the chemical composition or the physical arrangement or mixture of the composition
- B60C1/0025—Compositions of the sidewalls
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/013—Fillers, pigments or reinforcing additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L9/00—Compositions of homopolymers or copolymers of conjugated diene hydrocarbons
- C08L9/06—Copolymers with styrene
Abstract
A kind of rubber combination is disclosed, comprise: 100 mass parts rubber components (A), it comprises at least one in the group being selected from and being made up of natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, polybutadiene rubber and iso-butylene synthetic polyisoprene; With 1 to 60 mass parts lower molecular weight conjugated diolefine polymer (B), its have via gel permeation chromatography measure with the weight-average molecular weight 10 of polystyrene basis, 000 to 200,000 and vinyl bond content more than 40% in conjugated diene compound part, wherein said rubber components (A) comprises natural rubber and/polyisoprene rubber, and the per-cent of the styrene units in lower molecular weight conjugated diolefine polymer (B) is less than 5% quality.Described rubber combination workability in process of production and excellent heat resistance, and there is high Storage elastic modulus (G ') and low loss tangent (tan δ).
Description
Technical field
The present invention relates to rubber combination and use the tire of described rubber combination, relate more particularly to the workability of production period and excellent heat resistance, Storage elastic modulus (G ') is high and loss tangent (tan δ) is little rubber combination.
Background technology
Usually, when rubber combination is exposed to comparatively high temps between rubber combination curing time, or during in actual use as tire vulcanized rubber etc., produce rubber deterioration mainly through the crosslink part fracture in the rubber segment that sulfuration is formed.As the method for improvement of the resistance to rubber deterioration (thermotolerance) be exposed in comparatively high temps, it is effective for making the structure of the crosslink part in rubber segment be the technology of the key with large ionic dissociation energy.Particularly, address the compounding amount the technology increasing the compounding amount (so-called EV system) of vulcanization accelerator that reduce sulphur, this is because the thermotolerance of crosslink part is increased to monosulfidic bond (C-S-C) from polysulfidic bond (CSx-C) successively by disulfide linkage (C-S-S-C).But in the art, the thermotolerance of rubber is improved, but the bond distance of crosslink part in rubber segment shortens, and there is the problem of deteriorated elongation at break (Eb) or breaking tenacity (Tb).
Regulate and control trend correlation with improving the relevant whole world to Carbon emission to the concern of nearest environmental problem, the demand for the low fuel consumption of motor vehicle increases strongly.In order to meet this type of demand, require to reduce the rolling resistance as tyre performance.As the technology for reducing tire drag, the rubber combination with comparatively low loss tangent (tan δ) and low-heat-generation is used to be effective as the rubber combination being applied to tire face.
On the other hand, the rubber combination with high Storage elastic modulus (G ') is suitable as the rubber combination of the fetus face be applied in tire, sidewall and bead-core etc., therefore requires that exploitation has the rubber combination of low loss tangent (tan δ) and high Storage elastic modulus (G ').As the method for the Storage elastic modulus (G ') for improving rubber combination, the technology of the compounding amount of carbon black in known raising rubber combination, as bismaleimides (BMI) the such as N with ad hoc structure compounding disclosed in JP-A-2002-121326, N '-(4, 4 '-ditane)-bismaleimides etc. technology and disclosed in JP-A-2003-176378 the compounding technology with the compound such as two toxilic acid macrogol esters (PEGM) of the reactive group to rubber components and the adsorption group to filler (adsorptiongroup) etc.
But, when the compounding amount of the carbon black in rubber combination increases, the Storage elastic modulus (G ') of rubber combination can be improved, but the loss tangent of rubber combination (tan δ) increases simultaneously, thus the low-heat-generation of deteriorated rubber combination, in addition, the mooney viscosity of rubber combination increases, thus deteriorated processibility.
When will have to the reactive group of bismaleimides (BMI) or rubber components and to the compound of the adsorption group of filler compounding to rubber combination time, the Storage elastic modulus (G ') of rubber combination can be improved, the loss tangent (tan δ) of rubber combination is substantially equal with the loss tangent (tan δ) of the rubber combination without compound, and therefore the low-heat-generation of rubber combination can not be improved fully.
Summary of the invention
Therefore the object of the invention is to solve the problems referred to above of routine techniques, the workability of production period and excellent heat resistance, Storage elastic modulus (G ') is high and loss tangent (tan δ) is little rubber combination are provided.Equally, another object of the present invention is to provide at least fetus face, sidewall, air retaining wall, cord body coating rubber (ply-coatingrubber) and bead-core any one in use the pneumatic tyre of this rubber combination.
For achieving the above object, the present inventor carries out various research, discovery has specific weight-average molecular weight and vinyl bond content also suppresses the styrene units ratio contained extremely lower than in the compounding extremely specific rubber components of lower molecular weight conjugated diolefine polymer of certain value, to replace the part or all of tenderizer be generally used in rubber combination, thus, Storage elastic modulus (G ') is improved, loss tangent (tan δ) declines, thermotolerance can be improved and the workability of not deteriorated rubber combination in addition, and result completes the present invention.
Namely, rubber combination according to the present invention is characterised in that compounding 1 to 60 mass parts lower molecular weight conjugated diolefine polymer (B), based on 100 mass parts rubber components (A), described lower molecular weight conjugated diolefine polymer (B) have via gel permeation chromatography measure with the weight-average molecular weight 10 of polystyrene basis, 000 to 200, 000 and vinyl bond content in conjugated diene compound part be not less than 40%, described rubber components (A) comprises and is selected from by natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, at least one in the group of polybutadiene rubber and iso-butylene synthetic polyisoprene composition,
Wherein said rubber components (A) comprises natural rubber and/or polyisoprene rubber, and
In whole lower molecular weight conjugated diolefine polymer (B), the ratio of styrene units is less than 5 quality %.
In rubber combination according to the present invention, described rubber components (A) preferably have via gel permeation chromatography measure be greater than 200 with the weight-average molecular weight of polystyrene basis, 000.
In rubber combination according to the present invention, described lower molecular weight conjugated diolefine polymer (B) preferably have via gel permeation chromatography measure with the weight-average molecular weight of polystyrene basis for 20,000 to 200,000, more preferably 30,000 to 150,000.
In the preferred embodiment of rubber combination according to the present invention, the ratio of the styrene units in whole described rubber components (A) is less than 30 quality %.
In another preferred embodiment of rubber combination according to the present invention, described lower molecular weight conjugated diolefine polymer (B) is polyhutadiene and/or polyisoprene.Now, described lower molecular weight conjugated diolefine polymer (B) is preferably polyhutadiene.
In another preferred embodiment of rubber combination according to the present invention, further compounding carbon black or silicon-dioxide.
Equally, pneumatic tires according to the present invention be characterised in that at least fetus face, sidewall, air retaining wall, cord body coating rubber and bead-core any one in use aforementioned rubber composition.
According to the present invention, there is special ethylene bond content and weight-average molecular weight also suppresses the styrene units ratio contained to the lower molecular weight conjugated diolefine polymer being less than certain value by using, can provide rubber combination, the workability of its production period and excellent heat resistance, Storage elastic modulus (G ') is high and loss tangent (tan δ) is little.Equally, can provide at least fetus face, sidewall, air retaining wall, cord body coating rubber and bead-core any one in use the pneumatic tyre of this rubber combination.
Embodiment
Below in detail the present invention will be described.Rubber combination according to the present invention is characterised in that, compounding 1 to 60 mass parts lower molecular weight conjugated diolefine polymer (B), based on 100 mass parts rubber components (A), described lower molecular weight conjugated diolefine polymer (B) have via gel permeation chromatography measure with the weight-average molecular weight 10 of polystyrene basis, 000 to 200, 000 and vinyl bond content in conjugated diene compound part be not less than 40%, described rubber components (A) comprises and is selected from by natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, at least one in the group of polybutadiene rubber and iso-butylene synthetic polyisoprene composition,
Wherein said rubber components (A) comprises natural rubber and/or polyisoprene rubber, and
In whole lower molecular weight conjugated diolefine polymer (B), the ratio of styrene units is for being less than 5 quality %.
Usually, polydiene such as natural rubber or polyisoprene rubber etc. containing double bond on main chain are at high temperature easy to fracture as rubber components (A) and thermotolerance is low.But, rubber combination according to the present invention is compounding the lower molecular weight conjugated diolefine polymer (B) in conjugated diene compound part with high-vinyl linkage content, therefore, there is following effect: is formed by the crosslinked sulphur ruptured under being exposed to comparatively high temps and the carbon be present in lower molecular weight conjugated diolefine polymer (B) side chain in allyl group position and be cross-linked again.Thus, lower molecular weight conjugated diolefine polymer (B) can keep three-dimensional net structure with the crosslinked again of crosslinked sulphur, thus improves the thermotolerance of rubber combination.Equally, the present inventors have conducted studies and found that, when by have via gel permeation chromatography measure with the weight-average molecular weight 10 of polystyrene basis, 000 to 200, 000, vinyl bond content in conjugated diene compound part be not less than 40% and the ratio of styrene units in whole lower molecular weight conjugated diolefine polymer (B) to be less than the lower molecular weight conjugated diolefine polymer (B) of 5 quality % compounding in rubber combination, when being included in the part or all of tenderizer in formulation with replacement, Storage elastic modulus (G ') is improved, loss tangent (tan δ) can reduce, and the workability of not deteriorated rubber combination.
Rubber components (A) in rubber combination according to the present invention, for being selected from least one in the group that is made up of natural rubber, polyisoprene rubber (IR), styrene-butadiene copolymer rubber (SBR), polybutadiene rubber (BR) and iso-butylene synthetic polyisoprene (IIR), requires at least to comprise natural rubber and/or polyisoprene rubber.When rubber components (A) comprises styrene-butadiene copolymer rubber, the ratio of the styrene units in whole described rubber components (A) is preferably less than 30 quality %, be more preferably less than 20 quality %, be also more preferably less than 15 quality %.When the ratio of the styrene units in whole described rubber components (A) is less than 30 quality %, rubber components (A) is excellent with the consistency of lower molecular weight conjugated diolefine polymer (B).Therefore, the breaking tenacity (fracturestrength) of rubber combination increases, and stably can obtain the effect improving Storage elastic modulus (G ') and the angle tangent that reduces the wastage (tan δ).In addition, when lower molecular weight conjugated diolefine polymer (B) comprises styrene-butadiene copolymer, require that the ratio of styrene units in whole lower molecular weight conjugated diolefine polymer (B) is less than 5 quality %.And rubber components (A) can be used alone or uses with two or more blends.
According to the rubber components (A) of rubber combination of the present invention preferably have via gel permeation chromatography measure be greater than 200 with the weight-average molecular weight of polystyrene basis, 000.When the weight-average molecular weight with polystyrene basis is not more than 200, when 000, there is the worry of deteriorated rubber combination fracture characteristics.
Rubber combination according to the present invention needs to comprise 1 to 60 mass parts, preferably 5 to 50 mass parts, more preferably the lower molecular weight conjugated diolefine polymer (B) of 5 to 40 mass parts, based on 100 mass parts rubber components (A), described lower molecular weight conjugated diolefine polymer (B) have via gel permeation chromatography measure with the weight-average molecular weight 10 of polystyrene basis, 000 to 200, 000, vinyl bond content in conjugated diene compound part be not less than 40% and the ratio of styrene units in whole lower molecular weight conjugated diolefine polymer (B) be less than 5 quality %.When the amount of lower molecular weight conjugated diolefine polymer (B) is less than 1 mass parts, gives rubber combination weak with the effect of workability, and when it is more than 60 mass parts, there is the trend of deteriorated vulcanized rubber fracture characteristics.
Lower molecular weight conjugated diolefine polymer (B) need to have via gel permeation chromatography measure with the weight-average molecular weight 10,000 to 200,000 of polystyrene basis, preferably 20,000 to 200,000, more preferably 30,000 to 150,000, also more preferably 30,000 to 100,000.When the weight-average molecular weight with polystyrene basis is less than 10, when 000, the effect improving thermotolerance can not be obtained, and when it is more than 200, when 000, the workability deterioration of rubber combination.
Lower molecular weight conjugated diolefine polymer (B) needs the vinyl bond content had in conjugated diene compound part to be not less than 40%, is preferably not less than 45%, is more preferably not less than 50%.When the vinyl bond content in conjugated diene compound part is not less than 40%, obtain the effect improving thermotolerance.And when the vinyl bond content in conjugated diene compound part is less than 40%, be difficult to the thermotolerance guaranteeing rubber combination.
Lower molecular weight conjugated diolefine polymer (B) without particular limitation of, as long as it has specific weight-average molecular weight and the vinyl bond content in conjugated diene compound part, and suppress the styrene units ratio contained to being less than certain value, but the preferred homopolymer of conjugated diene compound or the multipolymer of aromatic vinyl compound and conjugated diene compound.As the conjugated diene compound of monomer, address 1,3-butadiene, isoprene, 1,3-pentadiene, 2,3-dimethylbutadienes, 2-phenyl-1,3-butadiene and 1,3-hexadiene etc.Wherein, 1,3-butadiene and isoprene are preferred.On the other hand, as the aromatic vinyl compound being used as monomer, vinylbenzene, p-methylstyrene, a vinyl toluene, p-tert-butylstyrene, alpha-methyl styrene, 1-chloro-4-methyl-benzene and Vinyl toluene etc. are addressed.Therefore, as lower molecular weight conjugated diolefine polymer (B), preferred polyhutadiene and/or polyisoprene, polyhutadiene is preferred.And these monomers may be used alone or in combination of two or more.
When lower molecular weight conjugated diolefine polymer (B) is for aromatic vinyl compound-conjugated diene compound multipolymer, the binding capacity of aromatic vinyl compound is preferably less than 5 quality %.When the binding capacity of aromatic vinyl compound is for being not less than 5 quality %, with rubber components (A), the ratio especially with the styrene units in whole rubber components (A) is less than the consistency deterioration of rubber components (A) such as natural rubber (NR) or the polyisoprene rubber (IR) of 30 quality %, can not obtain enough thermotolerances and fracture characteristics.
Lower molecular weight conjugated diolefine polymer (B) without particular limitation of, but its can such as by be only polymerized in the hydrocarbon solvent to polyreaction being inertia as monomer conjugated diene compound or polymerization obtain as the aromatic vinyl compound of monomer and the mixture of conjugated diene compound.When introducing at least one functional group in the molecule of lower molecular weight conjugated diolefine polymer (B), it can obtain by the following method: monomer polymerization starter is carried out (being total to) polymerization to produce (being total to) polymkeric substance with polymerization activity position by (1), then polymerization activity position is used the method for various improving agent modification, or (2) such as has the method for polymerization starter (being total to) polymerization single polymerization monomer of Sn-Li, C-Li or N-Li key with the polymerization starter with functional group.
As the polymerization starter for the synthesis of polymkeric substance (B), preferred lithium compound, further preferred hydrocarbyl lithium and lithium amide (lithiumamide) compound.When using lithium compound as polymerization starter, aromatic vinyl compound and conjugated diene compound are polymerized by anionoid polymerization.When hydrocarbyl lithium is used as polymerization starter, the polymkeric substance at the alkyl that acquisition has at polymerization starting terminal and the polymerization activity position at the other end.On the other hand, when lithium amide compound is used as polymerization starter, the polymkeric substance at the nitrogen-containing functional group that acquisition has at polymerization starting terminal and the polymerization activity position at the other end, described polymkeric substance can be used as the lower molecular weight conjugated diolefine polymer (B) in the present invention with at least one functional group, and without modifier modification.And it is in the scope of 0.2 to 20mmol that the consumption of polymerization starter is preferably based on every 100g monomer.
As hydrocarbyl lithium, address the reaction product etc. of lithium ethide, n-propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tertiary octyl group lithium, positive decyl lithium, phenyl lithium, 2-naphthyl lithium, 2-Butyl-hohenyl lithium, 4-phenyl-butyl lithium, cyclohexyl lithium, cyclopentyl lithium and di isopropenylbenzene and butyllithium.Wherein, lithium alkylide such as lithium ethide, n-propyl lithium, isopropyl lithium, n-Butyl Lithium, s-butyl lithium, tertiary octyl group lithium and positive decyl lithium etc. are preferred, and n-Butyl Lithium is particularly preferred.
As mentioned above, the method for producing conjugated diolefine polymer with above-mentioned polymerization starter without particular limitation of.Such as, polymkeric substance (B) can be produced by polymerization single polymerization monomer in the hydrocarbon solvent to polyreaction being inertia.As being the hydrocarbon solvent of inertia to polyreaction, address propane, normal butane, Trimethylmethane, Skellysolve A, iso-pentane, normal hexane, hexanaphthene, propylene, 1-butylene, iso-butylene, Trans-2-butene, cis-2-butene, 1-amylene, 2-amylene, 1-hexene, 2-hexene, benzene,toluene,xylene and ethylbenzene etc.They may be used alone or in combination of two or more.
Polyreaction needs to carry out under randomizer exists.The microstructure of the conjugated diene compound part in randomizer can control (being total to) polymkeric substance, more specifically has following effect: the content etc. controlling conjugated diene compound unit in the vinyl bond content of the conjugated diene compound part in (being total to) polymkeric substance or multipolymer and aromatic vinyl compound unit.As randomizer, address dimethoxy benzene, tetrahydrofuran (THF), glycol dimethyl ether, diethylene glycol dibutyl ether, diethylene glycol dimethyl ether, double tetrahydrofuran base propane, triethylamine, pyridine, N-methylmorpholine, N, N, N ', N '-tetramethylethylened, 1,2-dipiperidino ethane, tertiary amyl alcohol potassium (potassium-t-amylate), potassium tert.-butoxide (potassium-t-butoxide) and sodium tert-amyl alcohol etc.The consumption of randomizer is preferably in the scope of 0.01 to 100 molar equivalent, based on every 1 mole of polymerized initiator.
Anionoid polymerization is carried out preferably by solution polymerization.Monomer concentration in polymeric reaction solution is preferably at 5 to 50 quality %, more preferably within the scope of 10 to 30 quality %.In addition, when conjugated diene compound uses together with aromatic vinyl compound, the aromatic vinyl compound content in monomer mixture suitably can be selected according to the aromatic vinyl compound content of subject copolymers.And, polymerization system without particular limitation of, can be batch systems or continuous system.
Polymerization temperature in anionoid polymerization preferably at 0 to 150 DEG C, more preferably within the scope of 20 to 130 DEG C.And polymerization can be carried out under generation pressure (generatingpressure), but preferably usual be enough to keep use monomer to be substantially liquid phase pressure under carry out.When polyreaction is carried out under the pressure higher than generation pressure, reaction system is preferably pressurizeed with rare gas element.In addition, the parent material used in polymerization as monomer, polymerization starter and solvent etc. preferably in advance except dereaction interfering substance as water, oxygen, carbonic acid gas and protic compound etc. after use.
When having the polymerization activity position modifier modification of (being total to) polymkeric substance at polymerization activity position, nitrogenous compound, silicon-containing compound and sn-containing compound are preferably used as properties-correcting agent.In the case, nitrogen-containing functional group, siliceous functional group or stanniferous functional group introduce by modified-reaction.
The modified-reaction of polymerization activity position properties-correcting agent carries out preferably by solution reaction.The monomer for being polymerized can be comprised in this solution.And, the reaction system of modified-reaction without particular limitation of, can be batch systems or continuous system.In addition, the temperature of reaction of modified-reaction without particular limitation of, as long as reaction is carried out, temperature of reaction in the polymerization can adopt himself temperature.The consumption of properties-correcting agent, preferably in the scope of 0.25 to 3.0mol, more preferably 0.5 to 1.5mol, is used for the polymerization starter of (being total to) polymer production based on 1mol.
In the present invention, can be dry with isolating polymer (B) by the reaction solution comprising polymkeric substance (B), then can by compounding for resulting polymers (B) in rubber components (A), or the rubber cement of the rubber components (A) of the reaction solution with solution state that comprise polymkeric substance (B) can be mixed then dry, thus obtain the mixture of rubber components (A) and polymkeric substance (B).
In rubber combination according to the present invention, more preferably with the compounding filler of the amount of 30 to 90 mass parts, based on 100 mass parts rubber components (A).When the compounding amount of filler is less than 30 mass parts, the fracture characteristics of vulcanized rubber and wear resistant deficiency, and when it is more than 90 mass parts, workability is tending towards deterioration.As filler, preferred carbon black and silicon-dioxide.In addition, as carbon black, preferred FEF, SRF, HAF, ISAF and SAF carbon black grades, HAF, ISAF and SAF carbon black grades is preferred.On the other hand, as silicon-dioxide, preferred wet silicon dioxide (precipitatedsilica) and dry type silicon-dioxide (fumedsilica) etc., wet silicon dioxide is preferred.These reinforced fillings can be used alone, or combinationally use with two or more.
Tenderizer can be contained further according to rubber combination of the present invention.As tenderizer, address treated oil as paraffin oil, naphthenic oil and aromatics wet goods.Consider fracture characteristics and wear resistant, aromatic oil is preferred, considers low-heat-generation and cold property, and naphthenic oil and paraffin oil are preferred.The compounding amount of tenderizer without particular limitation of, but the compounding total amount of lower molecular weight conjugated diolefine polymer (B) and tenderizer is preferably 1 to 80 mass parts, based on 100 mass parts rubber components (A).When the compounding total amount of lower molecular weight conjugated diolefine polymer (B) and tenderizer is more than 80 mass parts, the fracture characteristics of vulcanized rubber is tending towards deterioration.
Except above-mentioned rubber components (A), lower molecular weight conjugated diolefine polymer (B), filler and tenderizer, within the scope without prejudice to the object of the present invention, suitably compoundingly the additive being generally used for rubber industry can be had as antioxidant, silane coupling agent, vulcanization accelerator, vulcanization accelerator additive (acceleratoractivator) and vulcanizing agent etc. according to rubber combination of the present invention.As these additives, those that be obtained commercially preferably can be used.Rubber combination is produced by following steps: by rubber components (A) and lower molecular weight conjugated diolefine polymer (B) and if the various additives of the suitable selection needed are compounding, mixing, heat refining (warming) and extruding.
Pneumatic tires according to the present invention be characterised in that at least fetus face, sidewall, air retaining wall, cord body coating rubber and bead-core any one in use aforementioned rubber composition.At least fetus face, sidewall, air retaining wall, cord body coating rubber and bead-core any one in use in the workability of tire at production period of this rubber combination, thermotolerance, low fuel consumption and driving stability excellent.Pneumatic tires according to the present invention without particular limitation of, as long as above-mentioned rubber combination be used at least fetus face, sidewall, air retaining wall, cord body coating rubber and bead-core any one in, this pneumatic tyre can be produced by common method.In addition, as the gas being fills up to tire, not only can use normal air or there is the air of oxygen partial pressure of adjustment, and rare gas element can be used as nitrogen, argon and helium etc.
" embodiment "
Provide the following example so that the present invention to be described, it is never intended to as restriction of the present invention.
The production example > of < polymkeric substance (B-1)
To drying and with nitrogen displacement 800mL pressure Glass Containers in load 300g hexanaphthene, 40g1,3-divinyl and 0.16mmol double tetrahydrofuran base propane, and again 1.32mmol n-Butyl Lithium (n-BuLi) is incorporated in wherein, then at 50 DEG C, carry out polyreaction 1.5 hours.In the case, polymerisation conversion is about 100%.Then, 2,6-, bis--t-butyl-p-cresol (BHT) solution in Virahol (BHT concentration: 5 quality %) 0.5mL is added to polymerization system, to stop polyreaction, dry according to usual mode further, to obtain polymkeric substance (B-1).
The production example > of < polymkeric substance (B-2)
To drying and with nitrogen displacement 800mL pressure Glass Containers in load 300g hexanaphthene, 40g1,3-divinyl, 10g vinylbenzene and 0.53mmol double tetrahydrofuran base propane, and again 1.32mmol n-Butyl Lithium (n-BuLi) is incorporated in wherein, then at 50 DEG C, carry out polyreaction 1.5 hours.In the case, polymerisation conversion is about 100%.Thereafter, 2,6-, bis--t-butyl-p-cresol (BHT) solution in Virahol (BHT concentration: 5 quality %) 0.5mL is added to polymerization system, to stop polyreaction, dry according to usual mode further, to obtain polymkeric substance (B-2).
The production example > of < polymkeric substance (B-3)
To drying and with nitrogen displacement 800mL pressure Glass Containers in load 300g hexanaphthene, 40g1,3-divinyl and 0.53mmol double tetrahydrofuran base propane, and again 1.32mmol n-Butyl Lithium (n-BuLi) is incorporated in wherein, then at 50 DEG C, carry out polyreaction 1.5 hours.In the case, polymerisation conversion is about 100%.Then, 2,6-, bis--t-butyl-p-cresol (BHT) solution in Virahol (BHT concentration: 5 quality %) 0.5mL is added to polymerization system, to stop polyreaction, dry according to usual mode further, to obtain polymkeric substance (B-3).
The production example > of < polymkeric substance (B-4)
To drying and with nitrogen displacement 800mL pressure Glass Containers in load 300g hexanaphthene, 40g1,3-divinyl and 0.79mmol double tetrahydrofuran base propane, and again 1.32mmol n-Butyl Lithium (n-BuLi) is incorporated in wherein, then at 50 DEG C, carry out polyreaction 1.5 hours.In the case, polymerisation conversion is about 100%.Then, 2,6-, bis--t-butyl-p-cresol (BHT) solution in Virahol (BHT concentration: 5 quality %) 0.5mL is added to polymerization system, to stop polyreaction, dry according to usual mode further, to obtain polymkeric substance (B-4).
The production example > of < polymkeric substance (B-5) to (B-11) and (B-17)
Except changing the consumption of n-Butyl Lithium (n-BuLi), the mode synthetic polymer (B-5) to (B-11) identical with the production example with polymkeric substance (B-3) and (B-17).
The production example > of < polymkeric substance (B-12) to (B-13)
Except changing the consumption of double tetrahydrofuran base propane, with the identical mode synthetic polymer (B-12) of the production example with polymkeric substance (B-1) to (B-13).
The production example > of < polymkeric substance (B-14) to (B-15)
Except changing 1,3-butadiene and cinnamic consumption, with the identical mode synthetic polymer (B-14) of the production example with polymkeric substance (B-2) to (B-15).
The production example > of < polymkeric substance (B-16)
1 is replaced except using isoprene, the consumption of double tetrahydrofuran base propane is also changed into 0.026mmol from 0.79mmol by 3-divinyl, and polyreaction is carried out beyond 7 hours, with the mode synthetic polymer (B-16) that the production example with polymkeric substance (B-4) is identical.
Weight-average molecular weight (Mw) and the microstructure of the polymkeric substance (B-1) to (B-17) of production described above are measured according to following methods.Result is shown in table 1.
(1) weight-average molecular weight (Mw)
With the weight-average molecular weight (Mw) of each polymkeric substance of polystyrene basis by gel permeation chromatography [GPC:HLC-8020, TOSOH manufactures, post: GMH-XL (two post series connection), TOSOH manufactures, detector: differential refractometer (RI)] measure as the standard of monodisperse polystyrene.
(2) microstructure
The microstructure of polymkeric substance is determined by infrared method (Mo Leiluo (Morello) method).
Table 1
| Weight-average molecular weight (Mw) (× 10 3) | Combined styrene content (quality %) | Vinyl bond content (%) | |
| Polymkeric substance (B-1) | 80 | 0 | 35 |
| Polymkeric substance (B-2) | 80 | 20 | 45 |
| Polymkeric substance (B-3) | 80 | 0 | 45 |
| Polymkeric substance (B-4) | 80 | 0 | 55 |
| Polymkeric substance (B-5) | 3 | 0 | 45 |
| Polymkeric substance (B-6) | 10 | 0 | 45 |
| Polymkeric substance (B-7) | 25 | 0 | 45 |
| Polymkeric substance (B-8) | 40 | 0 | 45 |
| Polymkeric substance (B-9) | 120 | 0 | 45 |
| Polymkeric substance (B-10) | 180 | 0 | 45 |
| Polymkeric substance (B-11) | 220 | 0 | 45 |
| Polymkeric substance (B-12) | 80 | 0 | 40 |
| Polymkeric substance (B-13) | 80 | 0 | 50 |
| Polymkeric substance (B-14) | 80 | 3 | 45 |
| Polymkeric substance (B-15) | 80 | 7 | 45 |
| Polymkeric substance (B-16) | 80 | 0 | 45 |
| Polymkeric substance (B-17) | 100 | 0 | 45 |
Then, preparation has the rubber combination of filling a prescription as shown in table 2-6, and measures mooney viscosity [ML1+4 (130 DEG C)] and the thermotolerance of rubber combination according to following methods.In addition, rubber combination is sulfuration at typical condition, to obtain vulcanized rubber, measures the Storage elastic modulus (G ') of vulcanized rubber thus, loss tangent (tan δ) and breaking tenacity according to following methods.Result is shown in table 2-6.
(3) mooney viscosity
Mooney viscosity [ML1+4 (130 DEG C)] is measured at 130 DEG C according to JISK6300-1:2001, and represent by based on following index: in table 2-5, the mooney viscosity of the rubber combination of comparative example 1 and 7 is 100, for embodiment in table 6 20 and comparative example 11, the mooney viscosity of the rubber combination in comparative example 11 is 100, for embodiment in table 6 21 and comparative example 12, the mooney viscosity of the rubber combination in comparative example 12 is 100, for embodiment in table 6 22 and comparative example 13, the mooney viscosity of the rubber combination in comparative example 13 is 100, for embodiment in table 6 23 and comparative example 14, the mooney viscosity of the rubber combination in comparative example 14 is 100.This index value is less, and workability is better.
(4) thermotolerance (reversion (vulcanizationreversion))
The moment of torsion of rubber combination is measured 15 minutes at 175 DEG C by using mobilometer (rheometer), to evaluate reversion according to following formula, it is based on following exponential representation: the reversion inverse (inversenumber) in the rubber combination showing comparative example 1 and 7 in 2-5 is 100, for the embodiment 20 in table 6 and comparative example 11, reversion inverse in rubber combination in comparative example 11 is 100, for the embodiment 21 in table 6 and comparative example 12, reversion inverse in rubber combination in comparative example 12 is 100, for the embodiment 22 in table 6 and comparative example 13, reversion inverse in rubber combination in comparative example 13 is 100, for the embodiment 23 in table 6 and comparative example 14, reversion inverse in rubber combination in comparative example 14 is 100.This index value is larger, and thermotolerance is better.
Reversion (%)=[(Fmax-F)/(Fmax-Fmin)] × 100
In the formula, Fmax represents the maximum value of moment of torsion, and Fmin represents the minimum value of moment of torsion, and F represents at the torque value of measurement after 15 minutes.
(5) Storage elastic modulus (G ') and loss tangent (tan δ)
Storage elastic modulus (G ') and loss tangent (tan δ) are at temperature 50 C, frequency 15Hz and strain 5% time, measured by the viscoelasticity measurement device using RHEOMETRICSCorporation to manufacture, and by representing based on following index: Storage elastic modulus (G ') and the loss tangent (tan δ) of the rubber combination in table 2-5 in comparative example 1 and 7 are 100 separately, for the embodiment 20 in table 6 and comparative example 11, the Storage elastic modulus (G ') of the rubber combination in comparative example 11 and loss tangent (tan δ) are 100 separately, for the embodiment 21 in table 6 and comparative example 12, the Storage elastic modulus (G ') of the rubber combination in comparative example 12 and loss tangent (tan δ) are 100 separately, for the embodiment 22 in table 6 and comparative example 13, the Storage elastic modulus (G ') of the rubber combination in comparative example 13 and loss tangent (tan δ) are 100 separately, for the embodiment 23 in table 6 and comparative example 14, the Storage elastic modulus (G ') of the rubber combination in comparative example 14 and loss tangent (tan δ) are 100 separately.About Storage elastic modulus (G '), index value is larger, and Storage elastic modulus (G ') is higher.About loss tangent (tan δ), index value is less, and low-heat-generation is better.
(6) breaking tenacity
Preparation JIS3 dumbbell (JISNo.3dumbbell) sample, and carry out tension test according to JISK6251-1993, to measure the breaking tenacity of rubber combination, it represents based on following index: in table 2-5, the breaking tenacity of the rubber combination of comparative example 1 and 7 is 100, for the embodiment 20 in table 6 and comparative example 11, the breaking tenacity of the rubber combination in comparative example 11 is 100, for the embodiment 21 in table 6 and comparative example 12, the breaking tenacity of the rubber combination in comparative example 12 is 100, for the embodiment 22 in table 6 and comparative example 13, the breaking tenacity of the rubber combination in comparative example 13 is 100, for the embodiment 23 in table 6 and comparative example 14, the breaking tenacity of the rubber combination of comparative example 14 is 100.This index value is larger, and breaking tenacity is better.
Table 2
Table 3
*1 with weight-average molecular weight=1 of polystyrene basis, and 500,000.
*2BR01, JSRCorporation manufacture, with weight-average molecular weight=550 of polystyrene basis, and 000.
*3N-(1,3-dimethylbutyl)-N '-phenyl-p-phenylene diamine.
*4 two-2-[4-morpholinodithio based bisulfide.
*5N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine.
As shown 2-3 finding, compared with the rubber combination of comparative example 1-6, the rubber combination of embodiment 1-7 of lower molecular weight conjugated diolefine polymer (B) is used to have the workability of high balance, thermotolerance, Storage elastic modulus (G '), loss tangent (tan δ) and breaking tenacity, described lower molecular weight conjugated diolefine polymer (B) has weight-average molecular weight 10,000-200,000, vinyl bond content in conjugated diene compound part be not less than 40% and its all in the ratio of styrene units be less than 5 quality %.
Table 4
Table 5
*6 natural rubbers, with the weight-average molecular weight of polystyrene basis (Mw)=1,500,000.
*7 polybutadiene rubbers, BR01, JSRCorporation manufacture, with the weight-average molecular weight of polystyrene basis (Mw)=550,000.
*8 styrene-butadiene copolymer rubber, SL563 type, JSRCorporation manufactures, with the weight-average molecular weight of polystyrene basis (Mw)=600 × 10
3, combined styrene content=20 quality %, vinyl bond content=55%.
*9 styrene-butadiene copolymer rubber, T0150, JSRCorporation manufacture, with the weight-average molecular weight of polystyrene basis (Mw)=900 × 10
3, combined styrene content=45 quality %, vinyl bond content=19%.
*10N-(1,3-dimethylbutyl)-N '-phenyl-p-phenylene diamine.
*11 2-2-[4-morpholinodithio based bisulfide.
*12N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine.
As shown 4-5 finding, the rubber combination using the vinyl bond content had in conjugated diene compound part to be less than the comparative example 8 of the lower molecular weight conjugated diolefine polymer (B-1) of 40% can not obtain enough thermotolerances and breaking tenacity.Equally, the rubber combination using the styrene units ratio had in they are whole to be not less than the lower molecular weight conjugated diolefine polymer (B-15) of 5 quality % and the comparative example 9 to 10 of (B-2) can not obtain enough thermotolerances and breaking tenacity.In addition, as the comparison finding of embodiment 15 and 17 to 19, the effect improving workability, thermotolerance, Storage elastic modulus (G '), loss tangent (tan δ) and breaking tenacity is increased sharply by the compounding amount increasing lower molecular weight conjugated diolefine polymer (B-17).
Table 6
*6 natural rubbers, with the weight-average molecular weight of polystyrene basis (Mw)=1,500,000.
*7 polybutadiene rubbers, BR01, JSRCorporation manufacture, with the weight-average molecular weight of polystyrene basis (Mw)=550,000.
*8 styrene-butadiene copolymer rubber, SL563 type, JSRCorporation manufactures, with the weight-average molecular weight of polystyrene basis (Mw)=600 × 10
3, combined styrene content=20 quality %, vinyl bond content=55%.
*9 styrene-butadiene copolymer rubber, T0150, JSRCorporation manufacture, with the weight-average molecular weight of polystyrene basis (Mw)=900 × 10
3, combined styrene content=45 quality %, vinyl bond content=19%.
*10N-(1,3-dimethylbutyl)-N '-phenyl-p-phenylene diamine.
*11 2-2-[4-morpholinodithio based bisulfide.
*12N-cyclohexyl-2-[4-morpholinodithio base sulfinyl amine.
As seen in Table 6, compared with the rubber combination of corresponding comparative example 11 to 14, improve workability, thermotolerance, Storage elastic modulus (G '), loss tangent (tan δ) and breaking tenacity by the rubber combination of the embodiment 20 to 23 formed by compounding for lower molecular weight conjugated diolefine polymer (B-17) rubber components (A) extremely containing styrene units.Equally, as the result finding from embodiment 20 to 23, when the ratio of the styrene units in whole described rubber components (A) is less than 30 quality %, sharply improve the workability of rubber combination, thermotolerance, Storage elastic modulus (G '), loss tangent (tan δ) and breaking tenacity.
Claims (8)
1. a rubber combination, it is characterized in that, compounding 1 to 60 mass parts lower molecular weight conjugated diolefine polymer (B), based on 100 mass parts rubber components (A), described lower molecular weight conjugated diolefine polymer (B) have via gel permeation chromatography measure with the weight-average molecular weight 40 of polystyrene basis, 000 to 100, 000 and vinyl bond content in conjugated diene compound part be not less than 50%, described rubber components (A) comprises and is selected from by natural rubber, polyisoprene rubber, styrene-butadiene copolymer rubber, at least one in the group of polybutadiene rubber and iso-butylene synthetic polyisoprene composition,
Wherein said rubber components (A) comprises natural rubber and/or polyisoprene rubber,
The ratio of the styrene units wherein in whole described rubber components (A) is less than 30 quality %, and
In whole described lower molecular weight conjugated diolefine polymer (B), the ratio of styrene units is less than 5 quality %.
2. rubber combination according to claim 1, wherein said rubber components (A) have via gel chromatography measure be greater than 200 with the weight-average molecular weight of polystyrene basis, 000.
3. rubber combination according to claim 1, wherein said lower molecular weight conjugated diolefine polymer (B) is polyhutadiene and/or polyisoprene.
4. rubber combination according to claim 3, wherein said lower molecular weight conjugated diolefine polymer (B) is polyhutadiene.
5. rubber combination according to claim 1, wherein further compounding carbon black or silicon-dioxide.
6. a pneumatic tyre, is characterized in that in fetus face, use the rubber combination according to any one of claim 1-5.
7. a pneumatic tyre, is characterized in that in sidewall, use the rubber combination according to any one of claim 1-5.
8. a pneumatic tyre, it is characterized in that at least air retaining wall, cord body coating rubber and bead-core any one in use rubber combination according to any one of claim 1-5.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2007055950 | 2007-03-06 | ||
| JP055950/2007 | 2007-03-06 | ||
| PCT/JP2008/053962 WO2008108408A1 (en) | 2007-03-06 | 2008-03-05 | Rubber composition and pneumatic tire comprising the same |
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| CN101663352A CN101663352A (en) | 2010-03-03 |
| CN101663352B true CN101663352B (en) | 2016-01-06 |
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| CN200880013148.1A Active CN101663352B (en) | 2007-03-06 | 2008-03-05 | Rubber combination and use its pneumatic tyre |
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| US (1) | US9879129B2 (en) |
| EP (1) | EP2119742B1 (en) |
| JP (1) | JP5436203B2 (en) |
| CN (1) | CN101663352B (en) |
| RU (1) | RU2429252C2 (en) |
| WO (1) | WO2008108408A1 (en) |
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| JP5580997B2 (en) * | 2009-03-13 | 2014-08-27 | 株式会社ブリヂストン | Rubber composition and tire |
| JP5436051B2 (en) * | 2009-05-29 | 2014-03-05 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| WO2010150347A1 (en) * | 2009-06-23 | 2010-12-29 | 株式会社ブリヂストン | Rubber composition and pneumatic tire comprising same |
| CN102369238B (en) * | 2009-06-26 | 2015-04-01 | 株式会社普利司通 | Rubber composition and tire comprising the same |
| US8404419B2 (en) * | 2010-05-12 | 2013-03-26 | Konica Minolta Business Technologies, Inc. | Electrostatic image developing toner |
| JP2012126795A (en) * | 2010-12-14 | 2012-07-05 | Bridgestone Corp | Rubber composition and tire using the same |
| JP2012131876A (en) * | 2010-12-21 | 2012-07-12 | Bridgestone Corp | Rubber composition and tire using the same |
| JP5831461B2 (en) * | 2010-12-24 | 2015-12-09 | 日本ゼオン株式会社 | Conjugated diene rubber, rubber composition, rubber cross-linked product, and tire |
| CN103717408B (en) * | 2011-07-28 | 2017-06-20 | 住友橡胶工业株式会社 | Pneumatic tire |
| JP5899011B2 (en) * | 2012-03-07 | 2016-04-06 | 株式会社ブリヂストン | POLYMER, RUBBER COMPOSITION CONTAINING THE POLYMER, AND TIRE HAVING THE RUBBER COMPOSITION |
| JP2013185059A (en) * | 2012-03-07 | 2013-09-19 | Bridgestone Corp | Polymer and producing method thereof, rubber composition containing the polymer, and tire having the rubber composition |
| JP6445916B2 (en) | 2015-04-01 | 2018-12-26 | 株式会社ブリヂストン | tire |
| JP5939333B1 (en) * | 2015-04-28 | 2016-06-22 | 宇部興産株式会社 | Method for producing diene rubber |
| KR101950705B1 (en) | 2015-11-30 | 2019-02-21 | 주식회사 엘지화학 | Preparation method low styrene butadiene rubber |
| JP6878813B2 (en) * | 2016-10-03 | 2021-06-02 | 住友ゴム工業株式会社 | Rubber composition for base tread |
| CN110546195B (en) * | 2017-04-25 | 2022-03-22 | 株式会社普利司通 | Rubber composition for run-flat tire and run-flat tire |
| WO2019116804A1 (en) | 2017-12-15 | 2019-06-20 | 株式会社ブリヂストン | Rubber composition and pneumatic tire |
| JP6849158B2 (en) * | 2018-10-16 | 2021-03-24 | 住友ゴム工業株式会社 | tire |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JPS5773030A (en) | 1980-09-20 | 1982-05-07 | Bridgestone Corp | Rubber composition for tire |
| JPH05148389A (en) * | 1991-10-29 | 1993-06-15 | Toyo Tire & Rubber Co Ltd | Vibrationproof rubber composition |
| JP3369278B2 (en) * | 1993-12-27 | 2003-01-20 | 株式会社ブリヂストン | Rubber composition |
| DE69612912T2 (en) * | 1995-06-30 | 2001-10-18 | Bridgestone Corp | Rubber compound and tires made from it |
| US5534592A (en) * | 1995-09-22 | 1996-07-09 | The Goodyear Tire & Rubber Company | High performance blend for tire treads |
| JP2002121326A (en) | 2000-10-19 | 2002-04-23 | Bridgestone Corp | Rubber composition and tire using the same |
| JP3902107B2 (en) | 2001-10-05 | 2007-04-04 | 株式会社ブリヂストン | Rubber composition |
| GB0129474D0 (en) * | 2001-12-08 | 2002-01-30 | Tun Abdul Razak Res Ct | Thermoplastic elastomer compositions |
| JP2004075960A (en) * | 2002-08-22 | 2004-03-11 | Jsr Corp | Elastomer composition for molded article containing continuous cell, molded article containing continuous cell and method for producing the same |
| JP2005047993A (en) * | 2003-07-30 | 2005-02-24 | Sumitomo Rubber Ind Ltd | Rubber composition for tire tread and pneumatic tire using the rubber composition |
| EP1535959B1 (en) * | 2003-11-28 | 2012-09-05 | Sumitomo Rubber Industries, Ltd. | Rubber composition for a tire and tire using the same |
| JP4113847B2 (en) | 2004-02-12 | 2008-07-09 | 住友ゴム工業株式会社 | Rubber composition and tire using the same |
| JP2005200598A (en) * | 2004-01-19 | 2005-07-28 | Toyo Tire & Rubber Co Ltd | Unvulcanized rubber composition to cover cord for belt of pneumatic tire and belt ply for pneumatic tire |
| JP4559167B2 (en) * | 2004-09-07 | 2010-10-06 | 住友ゴム工業株式会社 | Pneumatic tire |
| JP4911904B2 (en) | 2005-03-04 | 2012-04-04 | 株式会社ブリヂストン | Rubber composition and tire using the same |
| US8030406B2 (en) | 2005-03-04 | 2011-10-04 | Bridgestone Corporation | Rubber composition and pneumatic tire using the same |
| JP2006249230A (en) * | 2005-03-10 | 2006-09-21 | Bridgestone Corp | Rubber composition for tread and pneumatic tire using the same |
| CN101142268B (en) | 2005-03-14 | 2012-02-22 | 株式会社普利司通 | Rubber composition and pneumatic tire using the same |
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| WO2008108408A1 (en) | 2008-09-12 |
| US9879129B2 (en) | 2018-01-30 |
| RU2009136704A (en) | 2011-04-20 |
| EP2119742B1 (en) | 2013-04-24 |
| US20110190440A1 (en) | 2011-08-04 |
| EP2119742A4 (en) | 2012-01-18 |
| JPWO2008108408A1 (en) | 2010-06-17 |
| CN101663352A (en) | 2010-03-03 |
| EP2119742A1 (en) | 2009-11-18 |
| JP5436203B2 (en) | 2014-03-05 |
| RU2429252C2 (en) | 2011-09-20 |
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